WO2013065704A1 - フェノールスルホン酸アリールエステル、顕色剤および感熱記録材料 - Google Patents

フェノールスルホン酸アリールエステル、顕色剤および感熱記録材料 Download PDF

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WO2013065704A1
WO2013065704A1 PCT/JP2012/078096 JP2012078096W WO2013065704A1 WO 2013065704 A1 WO2013065704 A1 WO 2013065704A1 JP 2012078096 W JP2012078096 W JP 2012078096W WO 2013065704 A1 WO2013065704 A1 WO 2013065704A1
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Prior art keywords
group
compound
heat
recording material
sensitive recording
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PCT/JP2012/078096
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English (en)
French (fr)
Japanese (ja)
Inventor
荻野　明人
佳美 緑川
有希子 佐藤
圭一郎 稲田
麻衣 樋口
須賀　守
Original Assignee
日本製紙株式会社
株式会社エーピーアイ コーポレーション
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Application filed by 日本製紙株式会社, 株式会社エーピーアイ コーポレーション filed Critical 日本製紙株式会社
Priority to CN201280053323.6A priority Critical patent/CN104024220B/zh
Priority to IN3483DEN2014 priority patent/IN2014DN03483A/en
Priority to JP2013541796A priority patent/JP6184325B2/ja
Priority to KR1020147014350A priority patent/KR101668231B1/ko
Priority to BR112014010513A priority patent/BR112014010513B1/pt
Priority to US14/355,118 priority patent/US9073376B2/en
Priority to EP12846070.6A priority patent/EP2774916B1/en
Publication of WO2013065704A1 publication Critical patent/WO2013065704A1/ja

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds
    • B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
    • B41M5/3336—Sulfur compounds, e.g. sulfones, sulfides, sulfonamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/337—Additives; Binders
    • B41M5/3375—Non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/72—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/75—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/72—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/77—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing carboxyl groups bound to the carbon skeleton

Definitions

  • the present invention relates to a phenolsulfonic acid aryl ester useful as a developer.
  • the present invention further relates to a color developer and a heat-sensitive recording material containing the phenolsulfonic acid aryl ester.
  • a colorless or light-colored basic (electron-donating) leuco dye hereinafter may be abbreviated as “dye”
  • developer an electron-accepting developer
  • Thermally-sensitive recording materials having a thermal-sensitive recording layer mainly composed of “which may be abbreviated as“) are widely put into practical use.
  • a thermal printer or the like with a built-in thermal head is used. This thermal recording system is (a) no noise during recording, (b) no need for development and fixing, (c) maintenance-free, and (d) equipment compared to other recording systems that have been put to practical use.
  • the factor that greatly affects the color development sensitivity is the selection of the dye and developer (particularly the developer) constituting the heat-sensitive recording layer.
  • Various developers have been studied so far. For example, benzyl p-hydroxybenzoate, which has been expected as a high-sensitivity developer for a period of time, is no longer used because of its extremely low image storage stability.
  • bisphenol A ie, 4,4'-isopropylidene diphenol
  • image storability such as plasticizer resistance and heat resistance is not satisfactory.
  • bisphenol A is suspected of environmental hormone activity, there is a growing tendency to ban use worldwide. Some countries have actually banned the use of thermosensitive recording materials using bisphenol A.
  • bisphenol S ie, 4,4'-dihydroxydiphenyl sulfone
  • bisphenol S has the disadvantages that it has a high melting point and low color development sensitivity.
  • Patent Document 1 describes the use of an aryloxysulfonyl group-containing phenol derivative which may have a substituent as an electron-accepting compound (developer). Atoms, alkyl groups and the like are mentioned. However, Patent Document 1 does not describe an alkoxycarbonyl group or a carboxy group as a substituent of the aryl group. Further, as described in Patent Document 1, an aryloxysulfonyl group-containing phenol derivative having a chlorine atom or an alkyl group as a substituent of an aryl group has good color development sensitivity, but has poor background fogging, and has a blank paper portion. And the recording part have a disadvantage that the contrast becomes indistinct.
  • the present invention has been made paying attention to the above-described circumstances, and an object thereof is to provide a developer excellent in balance of color development sensitivity at low energy, background fogging and image storage stability. .
  • the phenolsulfonic acid aryl ester having a specific structure represented by the formula (1) is a developer excellent in the balance of color development sensitivity at low energy, background fogging and image storage stability. I found out.
  • the present invention based on this finding is as follows.
  • R 1 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group
  • m R 2 s independently represent an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group, a halogen atom, a hydroxy group, a cyano group, a nitro group, a carboxy group, or an amino group
  • n R 3 s independently represent an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group, a halogen atom, a hydroxy group, a cyano group, a nitro group, a carboxy group, or an amino group
  • m and n each independently represents an integer of 0 to 4.
  • thermosensitive recording material [5] The heat-sensitive recording material according to [4], wherein the heat-sensitive recording layer contains a second developer different from the compound according to [1] or [2].
  • the second developer is at least one selected from the group consisting of a bisphenol sulfone compound, a bisphenol compound, a urea compound, and a novolac phenol compound.
  • the thermosensitive recording layer is selected from the group consisting of 1,2-di (3-methylphenoxy) ethane, C10-21 fatty acid amide, ⁇ -benzyloxynaphthalene, diphenylsulfone and p-toluenesulfonamide.
  • the hindered phenol compound is at least one selected from the group consisting of a compound represented by formula (2), a compound represented by formula (3), and a compound represented by formula (4).
  • R 5 , R 8 and R 11 each independently represents an alkyl group
  • R 6 , R 7 , R 9 , R 10 , R 12 and R 13 each independently represent a hydrogen atom or an alkyl group.
  • the compound (1) (phenol sulfonic acid aryl ester) of the present invention as a color developer, it is excellent in the balance of color development sensitivity at low energy, background fogging and image preservability (heat resistance, plasticizer resistance, etc.).
  • a heat-sensitive recording material can be obtained.
  • R 1 in the formula (1) represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group.
  • the number of carbon atoms of the alkyl group represented by R 1 is preferably 1 to 8, more preferably 1 to 6, and still more preferably 1 to 4.
  • the alkyl group for R 1 may be linear, branched or cyclic.
  • the alkyl group for R 1 is preferably linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a sec-pentyl group, and a tert-pentyl group.
  • the carbon number of the alkenyl group of R 1 is preferably 2 to 8, more preferably 2 to 6, and further preferably 2 to 4.
  • the alkenyl group for R 1 may be linear, branched or cyclic.
  • the alkenyl group for R 1 is preferably linear or branched.
  • Examples of the alkenyl group include vinyl group, allyl group, isopropenyl group, 1-propenyl group, 2-butenyl group, 3-butenyl group, 1,3-butanedienyl group, 2-methyl-2-propenyl group and the like. Among these, a vinyl group and an allyl group are preferable.
  • the aryl group may be a single ring or a condensed ring.
  • the carbon number of the aryl group of R 1 is preferably 6 to 14, more preferably 6 to 10.
  • Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group, and among these, a phenyl group is preferable.
  • the aryl group may have 1 type or 2 or more types of substituent. Examples of the substituent for the aryl group include an alkyl group, an aryl group, a hydroxy group, a halogen atom, a nitro group, a carboxy group, and an amino group.
  • the carbon number of the aralkyl group of R 1 is preferably 7 to 15, more preferably 7 to 8.
  • Aralkyl groups include, for example, phenylmethyl (benzyl), phenylethyl (phenethyl), diphenylmethyl, 3-phenylpropyl, 2-phenylpropyl, 4-phenylbutyl, biphenylmethyl, naphthyl A methyl group etc. are mentioned, Among these, a benzyl group and a phenethyl group are preferable.
  • R 2 and R 3 in formula (1) are each independently an alkyl group, alkenyl group, aryl group, aralkyl group, alkoxy group, halogen atom, hydroxy group, cyano group, nitro group, carboxy group or amino group Indicates.
  • the description of the alkyl group, alkenyl group, aryl group, and aralkyl group of R 2 and R 3 is the same as described above.
  • the number of carbon atoms of the alkoxy group of R 2 and R 3 is preferably 1 to 8, more preferably 1 to 4.
  • the alkoxy group may be linear or branched.
  • Examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, pentoxy, isopentoxy, neopentoxy, tert-pentoxy, hexyloxy, iso
  • a hexyloxy group is exemplified, and among these, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a tert-butoxy group are preferable.
  • halogen atom examples include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.
  • a chlorine atom and a bromine atom are preferable.
  • M and n in the formula (1) each independently represents an integer of 0 to 4.
  • m and n being 0 means that R 2 and R 3 do not exist, respectively.
  • the m R 2 s may be the same as or different from each other.
  • the n R 3 s may be the same as or different from each other.
  • m is preferably 0 or 1, more preferably 0.
  • n is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.
  • R 1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aralkyl group having 7 to 8 carbon atoms
  • m R 2 s are each independently an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a carboxy group
  • n R 3 s are each independently an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a carboxy group
  • a combination in which m and n are each independently an integer of 0 to 2 is preferred;
  • R 1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aralkyl group having 7 to 8 carbon atoms
  • R 2 is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a carboxy group
  • n R 3 s are each independently an alkyl
  • Position of -CO-OR 1 group in the formula (1) when the 1-position carbon atom of group in the benzene ring with a -CO-OR 1 group (-O-) is bonded, preferably Is the 2nd or 4th position, more preferably the 2nd position.
  • the position of R 2 in formula (1) is not particularly limited.
  • the position of the —OH group in the formula (1) is preferably the 4-position when the carbon atom to which the sulfonyl group (—SO 2 —) in the benzene ring having the —OH group is bonded is the 1-position.
  • the position of R 3 is preferably the 3rd position or the 3rd position and the 5th position.
  • R 1 is an alkyl group having 1 to 6 carbon atoms
  • R 2 is an alkyl group having 1 to 6 carbon atoms
  • n R 3 s are each independently an alkyl group or carboxy group having 1 to 6 carbon atoms
  • m is an integer of 0 or 1
  • n is an integer from 0 to 2
  • the carbon atom to which the oxy group (—O—) in the benzene ring having a —CO—OR 1 group is bonded is the 1st position
  • the position of the —CO—OR 1 group is the 2nd position or the 4th position
  • a compound in which the position of the OH group is the 4-position when the carbon atom to which the sulfonyl group (—SO 2 —) in the benzene ring having the —OH group is bonded is the first position
  • Compounds represented by the following formulas (a1) to (a26) are more preferable.
  • compounds (a1) to (a5) and (a10) are more preferred from the viewpoint of color development sensitivity, background fogging and image storage stability, and compounds (a1) to (a3) and compound ( a5) is particularly preferred.
  • the purity of the compound (1) is usually 80 area% or more, preferably 90 area% or more, more preferably 94 area% or more.
  • area% means “area%” in the results of high performance liquid chromatography analysis.
  • the compound (1) of the present invention is obtained by reacting a compound represented by the formula (A) with a compound represented by the formula (B), for example, as shown below. It can be prepared by making (esterification) and then removing the R 4 group (deprotection).
  • the esterification of the compound (A) and the compound (B) can be performed according to a known method (for example, a method described in JP-A-2010-53128).
  • R 4 is a protecting group for a hydroxy group, and examples thereof include an acetyl group.
  • Deprotection of compound (C) can also be performed according to a known method.
  • the present invention also provides a developer for a heat-sensitive recording material containing the compound (1) (hereinafter sometimes abbreviated as “the developer of the present invention”). Only 1 type may be used for a compound (1) and it may use 2 or more types together.
  • the developer of the present invention may contain a developer other than the compound (1) (for example, a second developer described later).
  • the content of the compound (1) in the developer of the present invention is preferably 50% by weight or more, more preferably 60% by weight or more, and further preferably 70% by weight or more.
  • the present invention also provides a thermosensitive recording material having a support and a thermosensitive recording layer (thermosensitive coloring layer) provided on the support.
  • the heat-sensitive recording layer contains a colorless or light-colored basic (electron-donating) leuco dye and a developer for coloring the basic leuco dye, Contains compound (1).
  • compound (1) may be used alone or in combination of two or more.
  • the content of the compound (1) in the heat-sensitive recording layer is usually 0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight, particularly preferably 1 to 5 parts per 1 part by weight of the basic leuco dye. Parts by weight.
  • components other than the compound (1) (second developer, basic leuco dye, sensitizer, stabilizer, binder, cross-linking agent, pigment, lubricant, which can be used to form a heat-sensitive recording layer, Other additives) will be described in order.
  • components other than compound (1) all may use only 1 type and may use 2 or more types together.
  • the binder, the crosslinking agent, the pigment and the like can be used not only in the heat-sensitive recording layer but also in a layer other than the heat-sensitive recording layer (for example, a protective layer described later) that the heat-sensitive recording material of the present invention may have. .
  • the heat-sensitive recording layer may contain a second developer (preferably an electron-accepting developer) different from the compound (1) of the present invention as long as the effects of the present invention are not impaired.
  • a second developer preferably an electron-accepting developer
  • Any known developer in the field of conventional pressure-sensitive or thermal recording paper can be used as the second developer, and is not particularly limited. Only 1 type may be used for a 2nd color developer and it may use 2 or more types together.
  • the amount used is preferably 0.005 to 1 part by weight, more preferably 0.01 part by weight to 0.8 part by weight per 1 part by weight of the compound (1). Parts, more preferably 0.02 to 0.7 parts by weight.
  • thermosensitive recording material that maintains high color development sensitivity and further improves heat resistance, moisture resistance, and water-resistant image storage stability.
  • a bisphenol sulfone compound As the second developer of the present invention, a bisphenol sulfone compound, a bisphenol compound, a urea compound, and a novolac type phenol compound are preferable. Specific examples of typical developers are shown below.
  • ⁇ Bisphenolsulfone compound > 4,4′-dihydroxydiphenylsulfone, 2,4′-dihydroxydiphenylsulfone, 4-hydroxy-4′-propoxydiphenylsulfone, 4-hydroxy-4′-isopropoxydiphenylsulfone, 4-hydroxy-4′-allyloxy Diphenylsulfone, bis (3-allyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4′-benzyloxyphenylsulfone, 3,4-dihydroxyphenyl-4′-methylphenylsulfone, described in Japanese Patent No. 3913820 Bisphenol sulfone derivative, a bisphenol sulfone derivative described in Japanese Patent No. 4004289.
  • ⁇ Bisphenol compounds > 4,4'-isopropylidenediphenol, 2,2'-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy) Phenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 4,4′-dihydroxydiphenyl sulfide, di (4-hydroxy-3-methyl) described in Japanese Patent No. 4216325 Phenyl) sulfide, 2,2′-thiobis (3-tert-octylphenol), 2,2′-thiobis (4-tert-octylphenol).
  • ⁇ Urea compounds > 4,4′-bis (3- (phenoxycarbonylamino) methylphenylureido) diphenylsulfone, N- (p-toluenesulfonyl) -N ′-(3-p-toluenesulfonyloxyphenyl) described in Japanese Patent No. 4601174 Urea and its derivatives, 4,4′-bis (p-toluenesulfonylaminocarbonylamino) diphenylmethane.
  • thiourea compounds such as N, N′-di-m-chlorophenylthiourea, p-chlorobenzoic acid, stearyl gallate, zinc bis [4- (octyloxycarbonylamino) salicylate] dihydrate 4- [2- (p-methoxyphenoxy) ethyloxy] salicylic acid, 4- [3- (p-tolylsulfonyl) propyloxy] salicylic acid, 5- [p- (2-p-methoxyphenoxyethoxy) cumyl] salicylic acid
  • Aromatic carboxylic acids, and salts of these aromatic carboxylic acids with polyvalent metal salts such as zinc, magnesium, aluminum, calcium, titanium, manganese, tin, nickel, and further antipyrine complexes of zinc thiocyanate, terephthalaldehyde Complex zinc salt of acid and other aromatic carboxylic acid, JP-A-10-25857 Metal chelate complexes such as higher fatty acid metal
  • ⁇ Basic leuco dye> As the colorless or light-colored basic (electron-donating) leuco dye, any of those known in the field of conventional pressure-sensitive or heat-sensitive recording paper can be used and is not particularly limited. Dyes, fluoran leuco dyes, fluorene leuco dyes, divinyl leuco dyes and the like are preferable. Specific examples of typical colorless or light-colored dyes (dye precursors) are shown below. Moreover, these dyes (dye precursor) may use only 1 type, and may use 2 or more types together.
  • Triphenylmethane leuco dye 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide [also known as crystal violet lactone]; 3,3-bis (p-dimethylaminophenyl) phthalide [also known as malachite green lactone]
  • a known sensitizer may be used.
  • the sensitizer is not particularly limited.
  • 1,2-di (3-methylphenoxy) ethane, ⁇ -benzyloxynaphthalene, fatty acid amides having 10 to 21 carbon atoms (for example, stearic acid amide, palmitic acid amide, etc.), diphenyl sulfone, p-toluene Sulfonamides are preferred, 1,2-di (3-methylphenoxy) ethane, diphenylsulfone and p-toluenesulfonamide are more preferred, and 1,2-di (3-methylphenoxy) ethane showing high color development sensitivity even at low energy Is particularly preferred.
  • These sensitizers may use only 1 type and may use 2 or more types together.
  • the plasticizer resistance and heat resistance are further improved.
  • the amount used is usually 0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight, particularly preferably 1 to 5 parts by weight per 1 part by weight of the basic leuco dye. Part.
  • a stabilizer may be used to improve the image storage stability of the heat-sensitive recording material.
  • a stabilizer means an agent that has the effect of improving the storage stability of an image.
  • the stabilizer include hindered phenol compounds, ultraviolet absorbers (for example, benzophenone compounds and triazole compounds), and antioxidants.
  • the hindered phenolic compound improves the image storage stability (heat resistance, moisture resistance, water resistance, plasticizer resistance, etc.) of the recording area, and fading of the recording area (that is, over time due to long-term storage). This is preferable in terms of improving (decoloring).
  • the hindered phenol compound will be described.
  • the hindered phenol compound is a compound having usually 1 or more and 15 or less, preferably 2 or more and 6 or less hydroxyphenyl groups in one molecule.
  • the molecular weight of the hindered phenol compound is usually 200 or more and 2000 or less, preferably 250 or more and 1800 or less, more preferably 300 or more and 1500 or less.
  • the melting point of the hindered phenol compound is preferably 100 ° C. or higher and 300 ° C. or lower.
  • hindered phenol compounds examples include tris (hydroxyphenyl) alkanes and 1,1,3-tris substituted butane compounds described in JP-B-39-4469 or JP-A-56-40629. .
  • examples of the hindered phenol compound include a compound represented by the formula (2).
  • R 5 , R 8 and R 11 each independently represents an alkyl group
  • R 6 , R 7 , R 9 , R 10 , R 12 and R 13 each independently represent a hydrogen atom or an alkyl group.
  • the alkyl group of R 5 to R 13 may be any of linear, branched or cyclic. Specific examples of the alkyl group for R 5 to R 13 are the same as the specific examples of the alkyl group for R 1 .
  • the number of carbon atoms of the alkyl group of R 5 to R 13 is preferably 1 to 8. More preferably, the alkyl group of R 5 , R 8 and R 11 has 1 to 6 carbon atoms.
  • the number of carbon atoms of the alkyl group of R 6 , R 7 , R 9 , R 10 , R 12 and R 13 is more preferably 1-5.
  • R 6 , R 7 , R 9 , R 10 , R 12 and R 13 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is preferred.
  • R 6 , R 9 and R 12 are each a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and at least one of R 7 , R 10 and R 13 is a hydrogen atom is more preferable.
  • R 5 , R 8 and R 11 are the same, R 6 , R 9 and R 12 are the same, or R 7 , R 10 and R 13 are the same. More preferably, R 5 , R 8 and R 11 are the same, R 6 , R 9 and R 12 are the same, and R 7 , R 10 and R 13 are the same. R 5 , R 8 and R 11 are tert-butyl groups or cyclohexyl groups, R 6 , R 9 and R 12 are methyl groups, and R 7 , R 10 and R 13 are hydrogen atoms. Further preferred.
  • R 5 , R 8 and R 11 are tert-butyl groups, R 6 , R 9 and R 12 are methyl groups, and R 7 , R 10 and R 13 are hydrogen atoms
  • Adeka Tab AO-30 (trade name) manufactured by Adeka and OS-930 (trade name) manufactured by Osaka Shinyaku Co., Ltd. are commercially available.
  • Adeka Arcles DH-43 (trade name) manufactured by Adeka is commercially available.
  • these commercially available products can be particularly preferably used.
  • examples of the hindered phenol compound include compounds represented by the following formulas (3) to (9).
  • the compound (2) (in particular, R 5 , R 8 and R 11 are tert-butyl groups or cyclohexyl groups, and R 6 , R 9 and R 12 are methyl groups) , R 7 , R 10 and R 13 are hydrogen atoms (compound (2)), compound (3) and compound (4) are preferred.
  • the background fog can be improved.
  • the improvement of background fogging means that unintentional coloring of the blank paper portion due to heating or the like is suppressed.
  • hindered phenol compound Only one type of hindered phenol compound may be used, or two or more types may be used in combination.
  • the content thereof is preferably 0.001 to 2 parts by weight, more preferably 0.005 to 1 with respect to 1 part by weight of the compound (1). Part by weight, more preferably 0.01 to 0.5 part by weight. If the content of the hindered phenolic compound is less than this range, the moisture resistance, water resistance, and heat resistance of the recording area may decrease, the recording area may fade due to changes over time, and the color of the blank area due to heating May not be suppressed. On the other hand, when the amount is larger than the above range, there is a possibility that the coloring sensitivity is lowered and the plasticizer resistance of the recording portion is lowered.
  • a binder In order to form a heat-sensitive recording layer, it is preferable to use a binder.
  • the binder include fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, acetoacetylated polyvinyl alcohol, carboxy modified polyvinyl alcohol, amide modified polyvinyl alcohol, sulfonic acid modified polyvinyl alcohol, butyral modified polyvinyl alcohol, olefin modified polyvinyl alcohol, Nitrile modified polyvinyl alcohol, pyrrolidone modified polyvinyl alcohol, silicone modified polyvinyl alcohol, other modified polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, polystyrene, styrene-maleic anhydride copolymer, styrene-butadiene copolymer, etc.
  • Styrene copolymer ethyl cellulose and acetyl Cellulose derivatives such as cellulose, casein, arabic gum, oxidized starch, etherified starch, dialdehyde starch, esterified starch, polyvinyl chloride, polyvinyl acetate, polyacrylamide, polyacrylate, polyvinyl butyral, polyamide resin, silicone resin, Examples include petroleum resins, terpene resins, ketone resins, coumarone resins, and the like.
  • the amount of the binder used is suitably about 5 to 25% by weight in the solid content of the heat-sensitive recording layer.
  • Binders are generally used as solutions, emulsions, dispersions, pastes or combinations thereof.
  • Examples of the solvent of the solution, emulsion or dispersion, or the paste medium include water, alcohols, ketones, esters, and hydrocarbons.
  • Crosslinking agent examples include glyoxal, methylol melamine, melamine formaldehyde resin, melamine urea resin, polyamine epichlorohydrin resin, polyamide epichlorohydrin resin, potassium persulfate, ammonium persulfate, sodium persulfate, ferric chloride, Examples include magnesium chloride, borax, boric acid, alum, and ammonium chloride.
  • the amount used is preferably 0.01 to 10 parts by weight with respect to 1 part by weight of the basic leuco dye.
  • the pigment examples include inorganic or organic pigments such as silica (excluding colloidal silica), calcium carbonate, kaolin, calcined kaolin, diatomaceous earth, talc, titanium oxide, and aluminum hydroxide.
  • silica excluding colloidal silica
  • the amount used is usually 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight with respect to 1 part by weight of the basic leuco dye.
  • lubricant examples include fatty acid metal salts such as zinc stearate and calcium stearate, waxes, and silicone resins.
  • the amount used is preferably 0.01 to 10 parts by weight with respect to 1 part by weight of the basic leuco dye.
  • additives examples include a dispersant, an antifoaming agent, and a fluorescent dye.
  • the amount used is preferably 0.01 to 10 parts by weight with respect to 1 part by weight of the basic leuco dye.
  • ⁇ Support> There is no restriction
  • the shape of the support include a sheet shape, a roll shape, and a flat plate shape.
  • the support may have a single layer structure or a laminated structure.
  • the size of the support can be appropriately selected according to the intended use of the heat-sensitive recording material.
  • the thickness of the support is not particularly limited and may be appropriately selected depending on the purpose. It is preferably 30 to 2,000 ⁇ m, and more preferably 50 to 1,000 ⁇ m.
  • a protective layer may be provided on the heat-sensitive recording layer.
  • a protective layer is provided on the heat-sensitive recording layer to improve the image storage stability of the heat-sensitive recording material, the color development sensitivity at low energy is lowered.
  • the thermosensitive recording material of the present invention since the compound (1) is used as a developer, the color sensitivity at low energy is good even when a protective layer is provided on the thermosensitive recording layer.
  • the types and amounts of various components used in the protective layer are determined according to the required performance and recordability, and are not particularly limited.
  • an under layer mainly composed of a pigment and a binder can be provided between the support and the heat-sensitive recording layer for the purpose of further enhancing the color development sensitivity.
  • a back layer may be provided on the surface of the support opposite to the heat-sensitive recording layer.
  • an intermediate layer may be formed between the support and the under layer, between the thermosensitive recording layer and the protective layer, and between the support and the back layer.
  • the heat-sensitive recording material of the present invention comprises a coating solution containing a basic leuco dye and compound (1) and, if necessary, a second developer, a hindered phenol compound, a sensitizer, etc. at least on the support. It can be manufactured by coating and drying on one side to form a heat-sensitive recording layer.
  • This coating solution can be applied in accordance with a well-known conventional technique.
  • the application means for example, an off-machine coating machine or an on-machine coating machine equipped with various coaters such as an air knife coater, rod blade coater, vent blade coater, bevel blade coater, roll coater, curtain coater, etc. Can be used.
  • the coating liquid for forming the heat-sensitive recording layer may be, for example, a basic leuco dye, compound (1), and, if necessary, a second developer, a hindered phenol compound, a sensitizer, It can be formed by atomizing to a particle size of several microns or less by a pulverizer such as an attritor or a sand glider or a suitable emulsifying device, and then adding a binder or the like to them. Water, alcohols, etc. can be used as a solvent used for this coating liquid.
  • the solid content of the coating liquid is usually about 20 to 40% by weight.
  • the coating amount of the heat-sensitive recording layer can be appropriately selected depending on the composition and use of the heat-sensitive recording material, but is usually in the range of 1 to 20 g / m 2 , preferably 2 to 12 g / m 2 in terms of dry weight. .
  • the protective layer, the under layer, the back layer, and the intermediate layer can be formed by applying and drying a coating liquid containing the constituent components in the same manner as the heat-sensitive recording layer described above.
  • the heat-sensitive recording material of the present invention in which each layer is formed may be subjected to a process known in the field (for example, a smoothing process using a super calendar or the like).
  • thermosensitive coloring layer thermosensitive coloring layer
  • parts and % represent “parts by weight” and “% by weight”, respectively, unless otherwise specified.
  • the smoothness of the heat-sensitive recording material was measured according to JIS P8119 (Beck method). The higher the smoothness (second), the smoother the surface.
  • ⁇ Coating solution for thermal recording layer The following liquids A to E were separately wet ground with a sand grinder until the average particle diameter of each component became 0.5 ⁇ m.
  • the average particle diameter is an average diameter in a volume-based distribution, and was measured with a laser diffraction / scattering type particle size distribution measuring apparatus.
  • ⁇ Liquid A developer dispersion> Compound (a1): 6.0 parts Polyvinyl alcohol (10% aqueous solution): 18.8 parts Water: 11.2 parts ⁇ Liquid B (colorless basic leuco dye dispersion)> 3-Dibutylamino-6-methyl-7-anilinofluorane (manufactured by Yamamoto Kasei Co., Ltd., trade name “ODB-2”): 2.0 parts Polyvinyl alcohol (10% aqueous solution): 4.6 parts Water : 2.6 parts ⁇ Liquid C (sensitizer dispersion)> 1,2-di (3-methylphenoxy) ethane (trade name “KS-232” manufactured by Sanko Co., Ltd.): 6.0 parts Polyvinyl alcohol (10% aqueous solution): 18.8 parts Water: 11.2 Part ⁇ Liquid D (second developer dispersion)> Bis (3-allyl-4-hydroxyphenyl) sulfone (manufactured by N
  • Example 1 Each liquid was mixed in the following ratio to prepare a coating liquid 1 for a heat-sensitive recording layer.
  • Liquid A developer dispersion
  • Liquid B colorless basic leuco dye dispersion
  • Silica manufactured by Mizusawa Chemical Co., Ltd., trade name “P537”, 25% dispersion
  • Polyvinyl alcohol (10% aqueous solution) 25.0 parts
  • the under layer coating liquid was applied with a Meyer bar on one side of a high-quality paper (47 g / m 2 base paper) as a support so that the dry weight of the under layer was 10 g / m 2 and dried ( An under layer was formed by blowing and drying at 60 ° C. for 2 minutes.
  • the thermal recording layer coating liquid 1 was applied and dried (blow dryer, 60 ° C., 2 minutes) so that the dry weight of the thermal recording layer was 3.5 g / m 2 , and the thermal recording was performed.
  • a recording layer was formed.
  • the support on which the under layer and the heat-sensitive recording layer were formed was processed with a super calender so that the smoothness was 500 to 1000 seconds to obtain a heat-sensitive recording material.
  • thermosensitive recording material was produced in the same manner as in Example 1 except that the compound (a1) in the liquid A was changed to the compound (a2).
  • thermosensitive recording material was produced in the same manner as in Example 1 except that the compound (a1) in the liquid A was changed to the compound (a3).
  • thermosensitive recording material was produced in the same manner as in Example 1 except that the compound (a1) in the liquid A was changed to the compound (a5).
  • thermosensitive recording material was produced in the same manner as in Example 1 except that the compound (a1) in the liquid A was changed to the compound (a10).
  • thermosensitive recording material was produced in the same manner as in Example 1 except that the compound (a1) in the liquid A was changed to bisphenol A (ie, 4,4′-isopropylidenediphenol).
  • thermosensitive recording material was produced in the same manner as in Example 1 except that the compound (a1) in the liquid A was changed to 4-hydroxy-4′-isopropoxydiphenylsulfone.
  • thermosensitive recording material was produced in the same manner as in Example 1 except that the compound (a1) in the liquid A was changed to bisphenol S (that is, 4,4′-dihydroxydiphenyl sulfone).
  • thermosensitive recording material was produced in the same manner as in Example 1 except that the compound (a1) in the liquid A was changed to 4-hydroxy-4′-allyloxydiphenylsulfone.
  • thermosensitive recording material was produced in the same manner as in Example 1 except that the compound (a1) in the liquid A was changed to 4-hydroxybenzenesulfonic acid 4′-methylphenyl.
  • thermosensitive recording material was produced in the same manner as in Example 1 except that the compound (a1) in the liquid A was changed to 4-hydroxybenzenesulfonic acid 4′-tert-butylphenyl.
  • thermosensitive recording material was produced in the same manner as in Example 1 except that the compound (a1) in the liquid A was changed to 4-hydroxybenzenesulfonic acid 4′-chlorophenyl.
  • Example 6 The respective liquids were mixed at the following ratio to prepare a thermal recording layer coating solution 2.
  • Liquid A developer dispersion: 36.0 parts
  • Liquid B colorless basic leuco dye dispersion: 18.0 parts
  • Liquid C sensitizer dispersion: 36.0 parts
  • Silica Made by Mizusawa Chemical Co., Ltd., trade name “P537”, 25% dispersion
  • the under layer coating liquid was applied with a Meyer bar on one side of a high-quality paper (47 g / m 2 base paper) as a support so that the dry weight of the under layer was 10 g / m 2 and dried ( An under layer was formed by blowing and drying at 60 ° C. for 2 minutes.
  • the thermal recording layer coating liquid 2 was applied and dried (blow dryer, 60 ° C., 2 minutes) so that the dry weight of the thermal recording layer was 3.5 g / m 2 , and the thermal recording layer was heated.
  • a recording layer was formed.
  • the support on which the under layer and the heat-sensitive recording layer were formed was processed with a super calender so that the smoothness was 500 to 1000 seconds to obtain a heat-sensitive recording material.
  • thermosensitive recording material was produced in the same manner as in Example 6 except that 1,2-di (3-methylphenoxy) ethane in liquid C was changed to ⁇ -benzyloxynaphthalene.
  • thermosensitive recording material was produced in the same manner as in Example 6 except that 1,2-di (3-methylphenoxy) ethane in liquid C was changed to diphenylsulfone.
  • thermosensitive recording material was produced in the same manner as in Example 6 except that 1,2-di (3-methylphenoxy) ethane in liquid C was changed to stearamide.
  • thermosensitive recording material was produced in the same manner as in Example 6 except that the compound (a1) in the liquid A was changed to 4-hydroxy-4′-allyloxydiphenylsulfone obtained by the method described in Japanese Patent No. 2500532. .
  • thermosensitive recording material was produced in the same manner as in Example 6 except that ethane was changed to p-toluenesulfonamide.
  • Example 10 The liquids were mixed at the following ratios to prepare a thermal recording layer coating solution 3.
  • Liquid A developer dispersion: 25.2 parts
  • Liquid B colorless basic leuco dye dispersion: 18.0 parts
  • Liquid C sensitizer dispersion: 36.0 parts
  • Liquid D Silicone (manufactured by Mizusawa Chemical, trade name “P537”, 25% dispersion): 40.0 parts
  • the under layer coating liquid was applied with a Meyer bar on one side of a high-quality paper (47 g / m 2 base paper) as a support so that the dry weight of the under layer was 10 g / m 2 and dried ( An under layer was formed by blowing and drying at 60 ° C. for 2 minutes.
  • the thermal recording layer coating liquid 3 was applied and dried (blow dryer, 60 ° C., 2 minutes) so that the dry weight of the thermal recording layer was 3.5 g / m 2 , and the thermal recording was performed.
  • a recording layer was formed.
  • the support on which the under layer and the heat-sensitive recording layer were formed was processed with a super calender so that the smoothness was 500 to 1000 seconds to obtain a heat-sensitive recording material.
  • Example 11 Except that bis (3-allyl-4-hydroxyphenyl) sulfone in solution D was changed to 4-hydroxy-4′-allyloxydiphenylsulfone obtained by the method described in Japanese Patent No. 2500532, the same procedure as in Example 10 was performed. Thus, a heat-sensitive recording material was produced.
  • Example 12 Example 10 except that bis (3-allyl-4-hydroxyphenyl) sulfone in solution D was changed to 4-hydroxy-4′-propoxydiphenylsulfone (trade name “Tomilac KN” manufactured by API Corporation). In the same manner, a heat-sensitive recording material was produced.
  • thermosensitive recording material was produced in the same manner as in Example 10 except that bis (3-allyl-4-hydroxyphenyl) sulfone in the liquid D was changed to bisphenol S (4,4′-dihydroxydiphenylsulfone).
  • Example 14 Except that bis (3-allyl-4-hydroxyphenyl) sulfone in the liquid D was changed to bisphenol C (2,2′-bis (4-hydroxy-3-methylphenyl) propane), the same as in Example 10. Thus, a heat-sensitive recording material was produced.
  • thermosensitive recording material was produced in the same manner as in Example 10 except that bis (3-allyl-4-hydroxyphenyl) sulfone in the liquid D was changed to bisphenol A (4,4′-isopropylidenediphenol). .
  • Example 16 The bis (3-allyl-4-hydroxyphenyl) sulfone in the liquid D was changed to a phenol-formalin condensate described in International Publication No. 02/098767 (trade name “Tomilac 224” manufactured by API Corporation). A thermosensitive recording material was produced in the same manner as in Example 10 except that.
  • Example 17 Example 10 except that bis (3-allyl-4-hydroxyphenyl) sulfone in the liquid D was changed to a diphenylsulfone compound described in Japanese Patent No. 4004289 (trade name “Tomilac 214” manufactured by API Corporation). In the same manner, a heat-sensitive recording material was produced.
  • Example 18 The amount of liquid A was changed to 36.0 parts, and bis (3-allyl-4-hydroxyphenyl) sulfone in liquid D was converted to a diphenylsulfone compound described in Japanese Patent No. 4004289 (trade name “Tomilac” manufactured by API Corporation).
  • a thermosensitive recording material was produced in the same manner as in Example 10 except that the change was made to 214 ").
  • Example 19 The amount of liquid A was changed to 32.4 parts, and bis (3-allyl-4-hydroxyphenyl) sulfone in liquid D was converted to a diphenylsulfone compound described in Japanese Patent No. 4004289 (trade name “Tomilac” manufactured by API Corporation). 214 ”), and a heat-sensitive recording material was produced in the same manner as in Example 10 except that the amount of liquid D was changed to 3.6 parts.
  • Example 20 Implemented except that bis (3-allyl-4-hydroxyphenyl) sulfone in Liquid D was changed to the diphenylsulfone cross-linked compound described in Japanese Patent No. 3913820 (trade name “D-90” manufactured by Nippon Soda Co., Ltd.) In the same manner as in Example 10, a thermosensitive recording material was produced.
  • Example 21 The amount of liquid A was changed to 36.0 parts, and bis (3-allyl-4-hydroxyphenyl) sulfone in liquid D was converted to a diphenylsulfone crosslinked compound described in Japanese Patent No. 3913820 (manufactured by Nippon Soda Co., Ltd. A thermosensitive recording material was produced in the same manner as in Example 10 except that the change was made to D-90 ").
  • Example 22 The amount of liquid A was changed to 32.4 parts, and bis (3-allyl-4-hydroxyphenyl) sulfone in liquid D was converted to a diphenylsulfone bridged compound described in Japanese Patent No. 3913820 (trade name “Nippon Soda Co., Ltd. D-90 "), and a thermosensitive recording material was produced in the same manner as in Example 10 except that the amount of liquid D was changed to 3.6 parts.
  • Example 23 The amount of liquid A was changed to 36.0 parts, and bis (3-allyl-4-hydroxyphenyl) sulfone in liquid D was changed to 4,4′-bis (3- (phenoxycarbonylamino) methylphenylureido) diphenylsulfone.
  • a heat-sensitive recording material was produced in the same manner as in Example 10 except that the change was made.
  • Example 24 The amount of liquid A was changed to 36.0 parts, and bis (3-allyl-4-hydroxyphenyl) sulfone in liquid D was converted to N- (p-toluenesulfonyl) -N ′-( A thermosensitive recording material was produced in the same manner as in Example 10 except that 3-p-toluenesulfonyloxyphenyl) urea was used.
  • Example 25 The respective liquids were mixed at the following ratios to prepare a thermal recording layer coating liquid 4.
  • Liquid A developer dispersion: 36.0 parts
  • Liquid B colorless basic leuco dye dispersion: 18.0 parts
  • Liquid C sensitizer dispersion: 36.0 parts
  • Liquid E Dission of hindered phenolic compound: 3.6 parts
  • Silica manufactured by Mizusawa Chemical Co., Ltd., trade name “P537”, 25% dispersion
  • the under layer coating liquid was applied with a Meyer bar on one side of a high-quality paper (47 g / m 2 base paper) as a support so that the dry weight of the under layer was 10 g / m 2 and dried ( An under layer was formed by blowing and drying at 60 ° C. for 2 minutes.
  • the thermal recording layer coating liquid 4 was applied and dried (blow dryer, 60 ° C., 2 minutes) so that the dry weight of the thermal recording layer was 3.5 g / m 2 , and the thermal recording was performed.
  • a recording layer was formed.
  • the support on which the under layer and the heat-sensitive recording layer were formed was processed with a super calender so that the smoothness was 500 to 1000 seconds to obtain a heat-sensitive recording material.
  • Example 27 1,1,3-Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane in solution E is converted to 4,4′-butylidenebis (6-tert-butyl-3-methylphenol) (AP A thermal recording material was produced in the same manner as in Example 25 except that the product name was changed to “Yoshinox BB” manufactured by Corporation.
  • thermosensitive recording material was produced in the same manner as in Example 25 except that.
  • Example 29 A heat-sensitive recording material was produced in the same manner as in Example 25 except that the amount of liquid E was changed to 1.8 parts.
  • thermosensitive recording material was produced in the same manner as in Example 25 except that the amount of liquid A was changed to 35.64 parts and the amount of liquid E was changed to 0.36 parts.
  • thermosensitive recording material was produced in the same manner as in Example 25 except that the amount of liquid A was changed to 34.92 parts and the amount of liquid E was changed to 1.08 parts.
  • thermosensitive recording material was produced in the same manner as in Example 25 except that the amount of liquid A was changed to 34.2 parts and the amount of liquid E was changed to 1.8 parts.
  • thermosensitive recording material was produced in the same manner as in Example 25 except that the amount of liquid A was changed to 33.48 parts and the amount of liquid E was changed to 2.52 parts.
  • Example 34 The respective liquids were mixed at the following ratio to prepare a thermal recording layer coating liquid 5.
  • Liquid A developer dispersion: 36.0 parts
  • Liquid B colorless basic leuco dye dispersion: 18.0 parts
  • Liquid C sensitizer dispersion: 18.0 parts
  • Liquid E Hindered phenol compound dispersion: 1.8 parts
  • F liquid second sensitizer dispersion: 18.0 parts
  • Silica manufactured by Mizusawa Chemical, trade name “P537”, 25% dispersion
  • the under layer coating liquid was applied with a Meyer bar on one side of a high-quality paper (47 g / m 2 base paper) as a support so that the dry weight of the under layer was 10 g / m 2 and dried ( An under layer was formed by blowing and drying at 60 ° C. for 2 minutes.
  • the thermal recording layer coating liquid 5 was applied and dried (fan dryer, 60 ° C., 2 minutes) so that the dry weight of the thermal recording layer was 3.5 g / m 2 , and the thermal recording layer was heated.
  • a recording layer was formed.
  • the support on which the under layer and the heat-sensitive recording layer were formed was processed with a super calender so that the smoothness was 500 to 1000 seconds to obtain a heat-sensitive recording material.
  • thermosensitive recording material was produced in the same manner as in Example 34 except that 1,2-di (3-methylphenoxy) ethane in the liquid C was changed to diphenylsulfone.
  • thermosensitive recording material was produced in the same manner as in Example 34 except that p-toluenesulfonamide in the liquid F was changed to diphenylsulfone.
  • the heat-sensitive recording materials obtained in the examples and comparative examples were evaluated as follows.
  • ⁇ Color development sensitivity> A gradation pattern is printed using a thermal printer (TH-PMD) manufactured by Okura Electric Co., Ltd., and the Macbeth densitometer (image density and white paper density at applied energy of 0.26 mJ / dot and 0.35 mJ / dot) is measured. RD-914 using an amber filter). The results are shown in Tables 1 and 3-5.
  • Examples 1 to 5 using the compound (1) of the present invention as the developer are aryloxysulfonyl having an alkyl group or a chlorine atom instead of the —CO—OR 1 group.
  • Comparative Examples 5 to 7 using a group-containing phenol derivative corresponding to the developer described in Patent Document 1
  • the background fog was good and the contrast between the blank paper portion and the recording portion was clear.
  • Examples 1 to 8 had a higher image remaining ratio than Comparative Examples 5 to 7, and were excellent in durability against the plasticizer.
  • Examples 6 to 36 using the compound (1) of the present invention as a developer are also known in the case of heat-sensitive recording materials using a sensitizer. Compared with Comparative Examples 8 to 12 using the agent, the color development sensitivity at a low energy (applied energy of 0.26 mJ / dot) was high.
  • Examples 6 to 9 using a sensitizer in addition to the compound (1) of the present invention are also excellent in plasticizer resistance as compared with Comparative Examples 5 to 7. It was.
  • Examples 10 to 24 using a second developer, Examples 25 to 33 using a hindered phenol compound, and two sensitizers were used.
  • the used Examples 34 to 36 were further excellent in heat resistance, moisture resistance and water resistance.
  • Examples 34 to 36 were particularly excellent in heat resistance and plasticizer resistance.
  • the compound (1) of the present invention is a developer excellent in the balance of low energy color development sensitivity, background fogging and image storability (heat resistance, plasticizer resistance, moisture resistance, water resistance). In addition, it is possible to provide a heat-sensitive recording material which is excellent in suppressing fading of the recording portion.

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PCT/JP2012/078096 2011-10-31 2012-10-31 フェノールスルホン酸アリールエステル、顕色剤および感熱記録材料 WO2013065704A1 (ja)

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JP2018199663A (ja) * 2016-09-14 2018-12-20 三菱ケミカル株式会社 多価フェノール化合物およびその製造方法
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JP2019534189A (ja) * 2016-10-07 2019-11-28 ミツビシ ハイテク ペイパー ユーロップ ゲー・エム・ベー・ハーＭｉｔｓｕｂｉｓｈｉ ＨｉＴｅｃ Ｐａｐｅｒ Ｅｕｒｏｐｅ ＧｍｂＨ 感熱記録材料
JP7072130B1 (ja) * 2020-07-27 2022-05-19 日本製紙株式会社 感熱記録体
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JP2019534189A (ja) * 2016-10-07 2019-11-28 ミツビシ ハイテク ペイパー ユーロップ ゲー・エム・ベー・ハーＭｉｔｓｕｂｉｓｈｉ ＨｉＴｅｃ Ｐａｐｅｒ Ｅｕｒｏｐｅ ＧｍｂＨ 感熱記録材料
WO2019031525A1 (ja) * 2017-08-09 2019-02-14 三菱ケミカル株式会社 感熱記録材料及び積層体
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JPWO2019031525A1 (ja) * 2017-08-09 2020-08-20 三菱ケミカル株式会社 感熱記録材料及び積層体
JP7067559B2 (ja) 2017-08-09 2022-05-16 三菱ケミカル株式会社 感熱記録材料及び積層体
JP7072130B1 (ja) * 2020-07-27 2022-05-19 日本製紙株式会社 感熱記録体
JP2023067796A (ja) * 2021-10-29 2023-05-16 三光株式会社 新規な置換ヒドロキシ安息香酸エステル誘導体及びそれを用いた感熱記録材料
JP7321600B2 (ja) 2021-10-29 2023-08-07 三光株式会社 新規な置換ヒドロキシ安息香酸エステル誘導体及びそれを用いた感熱記録材料

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CN104024220A (zh) 2014-09-03
IN2014DN03483A (enrdf_load_stackoverflow) 2015-06-05
TW201323385A (zh) 2013-06-16
US20140315713A1 (en) 2014-10-23
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JP6184325B2 (ja) 2017-08-23
KR20140080557A (ko) 2014-06-30
US9073376B2 (en) 2015-07-07
KR101668231B1 (ko) 2016-10-21
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